WO2019051886A1

WO2019051886A1 - Amine polyether polyol, preparation method therefor, and application thereof

Info

Publication number: WO2019051886A1
Application number: PCT/CN2017/103950
Authority: WO
Inventors: 沈周峰; 朱霞林; 蔡仲铭
Original assignee: 万华化学集团股份有限公司; 万华化学（烟台）容威聚氨酯有限公司
Priority date: 2017-09-15
Filing date: 2017-09-28
Publication date: 2019-03-21
Also published as: CN107513157B; CN107513157A

Abstract

Provided is an amine polyether polyol, a preparation method therefor, and an application thereof. The preparation method for an amine polyether polyol provided by the present invention comprises the following steps: performing a self-catalyzed reaction on an aqueous solution of amine and part of an olefin oxide; then adding a catalyst; and adding the remaining olefin oxide for epoxidation with the amine, wherein the amine contains 90% (by mass) or more of phenylenediamine. By using an aqueous solution of phenylenediamine, the present preparation method for an amine polyether polyol avoids a high-temperature melting step, reduces production times and improves production efficiency, and, because initiation can be controlled to be carried out at a relatively low temperature, a high-performance product having a low K value, high strength, and excellent demolding performance is obtained.

Description

Amine polyether polyol and preparation method and application thereof

Technical field

The present invention relates to an amine-based polyether polyol and a process for the preparation thereof, and to a process for preparing a polyurethane foam using the amine-based polyether polyol.

Background technique

Polyether polyols are widely used in the preparation of polyurethane rigid foams and can be used as insulation materials in refrigerators, freezers, cold storages and the like.

The polyether polyol currently used is o-toluenediamine polyether polyol, and the price of its raw material o-toluenediamine has risen all the way in recent years, resulting in excessive cost. Therefore, it is imperative to develop alternatives. While phenylenediamine, especially o-phenylenediamine, is close to o-toluenediamine due to its structure and properties, it is expected to be developed as an alternative.

The preparation process of the ortho-phenylenediamine-based polyether polyols known at present is almost always prepared by adding o-phenylenediamine at a high temperature (melting point of 103 ° C) and then adding an oxidized olefin. In this method, since the melting temperature is too high, stirring cannot be started, and the initial melting of o-phenylenediamine is as long as several hours to several dozen hours, the production efficiency is low, and the cost is too high. In addition, due to the high temperature melting, the stirring cannot be turned on, and the local temperature of the raw material is too high, and side reactions such as carbonization and decomposition occur, and finally the final product has a darker color and poor quality. At the same time, in the high temperature state, o-phenylenediamine will undergo serious sublimation. Some of the o-phenylenediamine will adhere to the reactor wall after sublimation, and it will not participate in the reaction, which not only causes loss of raw materials but also affects the final product index and quality. In addition, the attachment of o-phenylenediamine to the wall of the vessel may cause difficulties in cleaning the reactor and affect the production of the next kettle product. In the application of the subsequent polyurethane foam, the polyether polyol is also used in the preparation of the polyether polyol, resulting in structural irregularities, low viscosity and the like, resulting in the final polyurethane product index, especially demolding, The K value and compressive strength are not as good as those of the o-toluenediamine polyether.

CN200980108998.4 discloses a method for synthesizing polyether polyol by using o-phenylenediamine as an initiator, which requires melting o-phenylenediamine at a high temperature, and the initial reaction temperature is high, causing inability to start stirring, and there are many vices. Reaction, and easy to cause loss of raw materials, obtained The polyether polyol is used in the polyether polyol which is not as good as the original toluene diamine as an initiator.

Further, in the conventional synthesis method involving the preparation of a polyether polyol by a polyamine, a solvent is rarely used, and water is never used as a solvent. Because in general, the addition of water will participate in the reaction of epoxy olefins, resulting in the formation of small molecular alcohols, which seriously affect product quality.

Summary of the invention

The present invention provides a novel method for preparing an amine-based polyether polyol, which can avoid the high-temperature melting step, improve production efficiency, reduce cost, and obtain a high-quality product.

In order to achieve the object, the technical scheme adopted by the present invention is as follows:

A first aspect of the present invention provides a method for preparing an amine-based polyether polyol, wherein an aqueous solution of an amine is subjected to an autocatalytic reaction with a portion of an olefin oxide, followed by adding a catalyst, and adding the remaining oxidized olefin to an amine for epoxidation; The amine contains 90% by mass or more of phenylenediamine. The present invention does not require high temperature melting in the early stage of the reaction.

Preferably, the phenylenediamine is at least one of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine, and more preferably o-phenylenediamine.

In the preparation of the amino polyether polyol, the amine is dissolved in water as an initial solvent, and the amine is preferably 90% by mass or more of o-phenylenediamine and 10% by mass or less of other amine compounds. Other amine compounds may include m-phenylenediamine, p-phenylenediamine, and the like. In a more preferred embodiment, the amine is a high purity (mass ratio greater than 99%) o-phenylenediamine.

In a preferred embodiment of the present invention, the autocatalytic reaction may be carried out at 130 ° C or lower in the autocatalytic reaction stage; more preferably, the autocatalytic reaction of the present invention may be carried out at a lower temperature, preferably below 105 ° C; further Preferably, the autocatalytic reaction of the present invention can also be carried out at a lower temperature, for example, below 95 ° C, or below 90 ° C, or at 70-95 ° C. The present invention employs an aqueous solution of an amine and an olefin oxide for autocatalytic reaction, and the initial reaction can be controlled at a relatively low temperature (for example, below 105 ° C, below 90 ° C, or preferably from 70 to 95 ° C; more preferably, the amine More preferably, o-phenylenediamine is used. In a further preferred embodiment, the autocatalytic reaction is carried out at a temperature below 100 ° C in an autocatalytic reaction. Thereafter, and before the addition of the catalyst, the reaction temperature may be raised to 100 ° C or higher to carry out an aging reaction, preferably 100 to 115 ° C, and the length of the aging reaction is preferably 0.5 to 1 h, but it is not necessary to carry out the aging reaction.

In the initial stage of the reaction, the present invention is an autocatalytic reaction of phenylenediamine, and water does not participate in the reaction. In a more preferred embodiment, the dehydration operation is carried out before the catalyst is added, or the dehydration operation is carried out before the addition of the oxidized olefin after the catalyst is added, thereby avoiding water participating in the subsequent reaction, reducing the occurrence of side reactions, and making the quality of the water to the final product. No effect. In the initial reaction stage, the initiator is an aqueous solution of an amine, and the initial reaction temperature can be carried out at a relatively low temperature, which reduces the sublimation of the raw material and avoids the loss of the raw material, thereby facilitating the obtaining of a structurally regular and highly viscous product. The properties of the subsequently prepared rigid polyurethane foam can be improved.

In a preferred embodiment of the invention, the amine is epoxidized with the remaining alkylene oxide at a temperature of from 100 ° C to 170 ° C, more preferably at a temperature of from 110 to 130 ° C; in some preferred embodiments, The reaction pressure can be controlled at 0.1-10 bar.

In a preferred embodiment of the invention, the molar ratio of a portion of the alkylene oxide to amine added prior to catalyst addition is from 1 to 4:1, preferably from 3 to 3.8:1.

Preferably, the amine polyether polyol has an equivalent weight of from 50 to 200, preferably from 80 to 125, per active hydrogen atom. In the reaction system, the ratio of the amount of the amine to the olefin oxide can be determined based on the equivalent.

Preferably, the oxidized olefin is one or a mixture of two of propylene oxide and ethylene oxide, more preferably propylene oxide.

The catalyst in the present invention may be a strong base or an amine catalyst, and the amount of the catalyst is preferably from 0.2 to 0.4% by weight based on the weight of the polyether polyol product. If a strong base is used as the catalyst, the catalyst is preferably removed after completion of the reaction, and the removal method is a conventional means in the art and will not be described again; for example, the catalyst can be removed by adding an appropriate amount of phosphoric acid and dehydrating filtration. The amine catalyst can be retained or removed as appropriate. Wherein, the strong base may be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, barium hydroxide or the like. The amine catalyst may be, for example, methylimidazole, N,N-dimethylcyclohexylamine, trimethylamine or the like.

The existing general process of adducts of o-phenylenediamine and alkylene oxide cannot be completely oxidized due to a part of the amine hydrogen under typical alkoxylation conditions, which leads to the formation of an average hydroxyl group, a small amount of a secondary amine group and a primary amine. The product of the base. Therefore each molecule has an average of 3-4 hydroxyl groups, Each molecule has 0-1 secondary amino groups, each having 0-0.1 primary amino groups. While the present invention ensures that the initial reaction (or initial reaction) is carried out at a lower temperature, the amount of secondary amine groups and primary amine groups in the product can be effectively reduced. The adduct prepared by the method of the present invention has an average of 3.5-4 hydroxyl groups, 0-0.5 secondary amino groups, and 0-0.05 primary amino groups per molecule. It is more likely that the adduct will have an average of 3.8-4 hydroxyl groups per molecule, 0-0.2 secondary amino groups, 0-0.01 primary amino groups. It is more likely that the adduct will have an average of 3.9-4 hydroxyl groups per molecule, 0-0.1 secondary amino groups, and 0-0.001 primary amino groups.

According to a second aspect of the present invention, there is provided an aminopolyether polyol obtained by the above production method.

The aminopolyether polyol prepared by the present invention may have a viscosity at 25 ° C of from 5,000 to 100,000 cps, preferably from 20,000 to 50,000 cps, more preferably from 30,000 to 4,000 cps.

A third aspect of the present invention provides a polyol composition for producing a polyurethane foam, the polyol composition comprising 10% by mass or more of the aminopolyether polyol as described above, more preferably Containing 30-60% by mass of the aminopolyether polyol as described above. Of course, the polyol composition may also contain only the aminopolyether polyols described above.

As a preferred embodiment, the polyol composition further contains one or more of a polyester polyol and other polyether polyols. In some aspects, the polyester polyol can be used as an additional polyol. The other polyether polyol may contain a polyether polyol which is an initiator (or initiator), and the initiator may be, for example, an alkylene glycol (eg, ethylene glycol, propylene glycol, 1, 4). -butanediol, etc.), glycol ether (such as diethylene glycol, triethylene glycol, etc.), glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, etc.; the initiator may also contain primary/secondary amino groups. A compound such as ethylenediamine, diethanolamine, o-toluenediamine or the like. More preferably, the other polyether polyol comprises a polyether polyol having sucrose as an initiator (or as a starter), preferably in an amount of 15-40% by mass, more preferably, of the polyol composition. It is 20-40% by mass, and more preferably 25-35% by mass.

The other polyether polyols may also include one or more of oleyl ether and a polyether polyol starting with MDA-100. The oil ether is a fatty acid ester-containing polyol, and the initiator is preferably sucrose, diethylene glycol and various fatty acid esters, by adding propylene oxide or epoxy B. Alkane or a mixture of the two. The fatty acid esters may include various animal and vegetable fats, and some chemical synthetic fatty acid esters, such as palm oil, castor oil, soybean oil, linseed oil, and purified waste oil. The amount of the oleyl ether is preferably from 5 to 40% by mass, more preferably from 5 to 30% by mass, still more preferably from 10 to 20% by mass, still more preferably from 10 to 15% by mass. The polyether polyol starting from MDA-100 is an adduct of 4,4'-diaminodiphenylmethane with propylene oxide/ethylene oxide or a mixture of the two, preferably in an amount of a polyol composition. 0 to 30% by mass, more preferably 10 to 30% by mass, still more preferably 15 to 25% by mass.

Further preferably, the other polyether polyol is a mixture of one or more of oleyl ether, a polyether polyol having sucrose as a starter, and a polyether polyol having MDA-100 as a starter.

More preferably, the polyol composition comprises the following components by mass percentage: 30-60% of the amino polyether polyol described above, polyether polyol 15-40 with sucrose as the initiator %, polyether polyol having MDA-100 as a starting agent 0-30% (more preferably 10-30%), and oleyl ether 5-40%. With the preferred combination, the cost can be effectively controlled, and a better product viscosity can be obtained, and the obtained product can also perform well.

A fourth aspect of the invention provides a method of preparing a polyurethane foam, comprising the steps of:

1) forming a mixture comprising: a polyol composition as hereinbefore described, at least one blowing agent, at least one polyisocyanate, at least one catalyst, at least one surfactant;

2) The mixture is placed under conditions such that the mixture reacts to expand and solidify to form a rigid polyurethane foam. The specific process operation for preparing the rigid polyurethane foam is a conventional technical means in the art, and is not particularly limited. The conventional operation can be carried out by referring to preparing a constant temperature mold having a desired size and shape, and the mold has one or A plurality of material injection ports, and usually one or more air outlet holes in the mold, and then the above mixture is injected into the mold, and the mixture is reacted and expanded in the mold cavity to form a polyurethane foam.

In a preferred embodiment of the invention, the polyisocyanate is used in an amount of from 1.0 to 1.3, preferably from 1.1 to 1.2, based on the equivalent of the polyol composition; and the amount of the blowing agent is from 10 to 20 parts, preferably based on 100 parts by weight of the polyol composition. 13-17 parts; based on 100 parts by weight of polyol The composition is used in an amount of from 1 to 4 parts, preferably from 1.5 to 3 parts; based on 100 parts by weight of the polyol composition, the surfactant is used in an amount of from 0.01 to 6 parts, preferably from 2 to 4 parts.

The polyisocyanate may include at least one of an aromatic, aliphatic, and alicyclic polyisocyanate. Preferred are aromatic polyisocyanates such as 2,4- and/or 2,6-toluene diisocyanate, various isomers of diphenylmethane diisocyanate, hexahydrotoluene diisocyanate, methoxyphenyl-2,4 - Diisocyanate, hydrogenated MDI, polymethylene polyphenyl isocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, toluene-2,4,6-triisocyanate, and the like. A preferred polyisocyanate is a polymeric MDI which is a mixture of polymethylene polyphenyl polyisocyanates of monomeric MDI.

The blowing agent used may be water or at least one physical blowing agent. The physical blowing agent may be a mixture of one or more of a hydrocarbon, an alkane, a fluorocarbon, a dialkyl ether, and the like. A more preferred blowing agent may be a CP (cyclopentane) blowing agent.

The catalyst used in the preparation of the polyurethane foam may include various amines or organotin catalysts. It preferably includes a tertiary amine catalyst such as triethylenediamine, dimethylbenzylamine, pentamethyldiethylenetriamine, dimethylethylamine, N-alkyldimethylamine compound and the like.

The surfactant used may be selected from the alkali metal and amine salts of fatty acids, castor oil, ricinoleic acid, siloxane-oxyalkylene polymers or copolymers, oxyethylated alkylphenols, peanut oil , paraffin, fatty alcohol, etc. Organosiloxanes are preferred.

The technical solution provided by the invention has the following beneficial effects:

The preparation method of the amino-based polyether polyol provided by the invention has no high-temperature melting step, can greatly save production time, improve production efficiency and reduce cost. Compared with the traditional high-temperature melting of o-phenylenediamine to produce amine-based polyether polyols, it can save about 5 hours of production time and increase production efficiency by nearly one-fifth.

The present invention can carry out an autocatalytic reaction (initial reaction) at a relatively low temperature, and the temperature can be controlled even below 95 ° C, which can avoid many problems caused by a high initial reaction temperature and can reduce side reactions. Since the initial reaction is an autocatalytic reaction and can be carried out at a relatively low temperature, many disadvantages caused by high-temperature melting can be avoided, thereby obtaining a high-performance product having not only a lower K value but also a higher compressive strength. And also has superior release properties. At the same time, the obtained product has a lighter shade, a regular structure and a high viscosity.

The polyurethane-based polyether polyol produced by the process of the invention has a rigid polyurethane foam which is not inferior in overall performance to the foam of the conventional o-toluenediamine polyether, even in certain properties. It is also stronger than previous products. The polyether polyol prepared by the process of the invention can completely replace the original o-toluenediamine polyether, and can even give the product a better K value, compressive strength and mold release performance. The polyurethane foam prepared by the invention can be used for producing thermal insulation layers of refrigerators, refrigerators, refrigerated containers, water heaters and the like.

Detailed ways

In order to better understand the technical solution of the present invention, the content of the present invention will be further clarified below with reference to the embodiments, but the content of the present invention is not limited to the following embodiments.

The test methods used or possible in the following examples are described below:

1. Test method for polyol properties

GB/T 12008.3-2009 is used to determine the hydroxyl value of polyether polyols;

GB/T10008.7-2010 is used to determine the viscosity of polyether polyols;

GB/T9724-2007 is used to determine the pH of polyether polyols;

GB/T12008.4-2009 is used to determine the K ⁺ of polyether polyols;

GB/T22313-2008 is used to determine the moisture of polyether polyols.

2. Test methods for foam properties

QB/JH is used to test the release properties of the foam;

GB/T 10295-2009 for testing the K factor of foam;

GB/T 8813-2008 is used to test the strength of foam.

Example 1

Example 1 is a comparative example in which a polyether polyol was prepared using o-phenylenediamine, and o-phenylenediamine was melted by a high-temperature melting method. Follow the steps below:

O-phenylenediamine (570 g, 5 mol) was added to the reaction vessel, and the test pressure was replaced by nitrogen. The temperature of the kettle was set to 110 ° C, and the stirring was heated for 1 h (this period of time was found to be more than 6 hours to complete the melting). The olefin oxide (specifically propylene oxide) was metered in at a flow rate of 800 g/h until a total of 1015 g (17.5 mol) of alkylene oxide was added to the reaction vessel. Then continue the reaction for 2 h. Then add 20g of potassium hydroxide aqueous solution (concentration is 50wt%). The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of an aqueous phosphoric acid solution having a mass concentration of 50% was added to remove K ions, thereby obtaining a final product polyol. The resulting polyol had an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.65 per molecule, a secondary amine group content of 0.27, a primary amine group content of less than 0.04, and a viscosity of 18416 cps at 25 °C.

Example 2

Example 2 is an example of the preparation of an amine polyether polyol using the process of the present invention. Follow the steps below:

Water (135g, 7.5mol) and o-phenylenediamine (570g, 5mol) were added to the reaction vessel, and the pressure was replaced by nitrogen. The stirring was heated to 90 ° C. When the temperature was raised to 90 ° C, o-phenylenediamine was obtained. The aqueous solution (and in the amplification experiment, it is only necessary to continue to stir for 1 hour after the temperature is raised to 90 ° C to completely dissolve). The oxidized olefin (specifically propylene oxide used in this example) was metered in at a flow rate of 800 g/h until a total of 1015 g (17.5 mol) of alkylene oxide was added to the reaction vessel. The autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of a 50 wt% aqueous phosphoric acid solution was added to remove the K ion, and the treatment yielded the final product amino polyether polyol. The resulting amino polyether polyol has an equivalent weight of 89 per active hydrogen atom, a hydroxyl group content of 3.84 per molecule, a secondary amine group content of 0.108, a primary amine group content of less than 0.003, and a viscosity at 25 ° C. 34553cps.

Example 3

Example 3 is an example of the preparation of an amino polyether polyol using the process of the present invention. Follow the steps below:

Water (135g, 7.5mol) and o-phenylenediamine (570g, 5mol) were added to the reaction vessel, and the pressure was replaced by nitrogen. The stirring was heated to 85 ° C. When the temperature was raised to 85 ° C, o-phenylenediamine was obtained. Aqueous solution (and in the amplification experiment, it only needs to be after the temperature rises to 85 ° C) Continue to stir for 1.5h to completely dissolve). The oxidized olefin (specifically propylene oxide used in this example) was metered in at a flow rate of 700 g/h until a total of 1015 g (17.5 mol) of alkylene oxide was added to the reaction vessel. The autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of a 50 wt% aqueous phosphoric acid solution was added to remove the K ion, and the treatment yielded the final product amino polyether polyol. The resulting amino polyether polyol has an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.87 per molecule, a secondary amine group content of 0.106, a primary amine group content of less than 0.002, and a viscosity at 25 ° C. 35822cps.

Example 4

Example 4 is an example of the preparation of an amino polyether polyol using the process of the present invention. Follow the steps below:

Water (135g, 7.5mol) and o-phenylenediamine (570g, 5mol) were added to the reaction vessel, and the pressure was replaced by nitrogen. The stirring was heated to 90 ° C. When the temperature was raised to 90 ° C, o-phenylenediamine was obtained. The aqueous solution (and in the amplification experiment, it is only necessary to continue to stir for 1 hour after the temperature is raised to 90 ° C to completely dissolve). The oxidized olefin (specifically propylene oxide used in this example) was metered in at a flow rate of 800 g/h until a total of 1102 g (19 mol) of alkylene oxide was added to the reaction vessel. The autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1,102 g (19 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of a 50 wt% aqueous phosphoric acid solution was added to remove the K ion, and the treatment yielded the final product amino polyether polyol. The resulting amino polyether polyol has an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.85 per molecule, a secondary amine group content of 0.107, a primary amino group content of less than 0.003, and a viscosity at 25 ° C. 37462cps.

Example 5

Example 5 is a comparative example, using o-toluenediamine production commonly used in the prior art. Polyol, in order to make a better comparison with Example 2, solvent water was introduced in this Example 5, and in the prior art, no solvent was often added. This embodiment specifically follows the steps as follows:

Water (135 g, 7.5 mol) and o-toluenediamine (630 g, 5.16 mol) were added to the reaction vessel, and the test pressure was replaced with nitrogen, and the mixture was heated to 90 ° C with stirring. The olefin oxide was metered in at a flow rate of 800 g/h until a total of 930 g (16 mol) of alkylene oxide was added to the reaction vessel. After 1 h of reaction, the temperature was raised to 105 ° C and further reacted for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1328 g (22.9 mol) of olefin oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of a 50 wt% aqueous phosphoric acid solution was added to remove K ions, and the final product polyol was obtained by treatment. The resulting polyol had an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.65 per molecule, a secondary amine group content of 0.088, a primary amine group content of less than 0.002, and a viscosity at 25 ° C of 25633 cps.

Comparing Example 1 with Example 2, in Example 1, the o-phenylenediamine was melted at a high temperature without solvent addition, and it was found that the initial reaction could not be stirred during the preparation, and the obtained product was darker than that of Example 2. And the viscosity is far below the requirement, much lower than the product of Example 2. It was also found in the amplification experiment that the melting time of o-phenylenediamine in Example 1 needs to be more than 6 hours; and in the case of the amplification experiment of Example 2, there is no case where the dissolution time is prolonged excessively (when the temperature is raised to 90 ° C) It takes only 1 hour to completely dissolve).

Comparing Example 5 with Example 2, the o-toluenediamine of Example 5 was used in the prior art to prepare a polyether polyol, usually without solvent (including water). In the fifth embodiment, water was introduced therein, and it was found that the performance of the o-toluenediamine polyether polyol prepared by the prior art anhydrous process was significantly reduced, and the viscosity was much lower than that of the existing anhydrous process. Due to the introduction of water, the side reaction is increased. However, in Example 2 of the present invention, although water was introduced as a solvent, the properties of the product were superior, and the viscosity was comparable to that of the conventional polyether polyol prepared by o-toluenediamine.

Example 6-12

Examples 6-12 are examples of the preparation of rigid polyurethane foams. Adopt the following table 1 The formulation produced the rigid polyurethane foam of Examples 6-12, wherein the formulations of the examples also contained a polyisocyanate (not shown in Table 1), and the polyisocyanate was used in an amount of 1.2 times the polyol equivalent. The rigid polyurethane foams of Examples 6-12 were prepared by the following method: Mixture of Table 1 and polyisocyanate (temperature control 21 ° C), using a high pressure machine injection molding machine (Krauss Maffei RSC 16/16) at 180-220 m/ The rate of s is processed, and then injected into a mold of constant temperature (35 ° C) to carry out a reaction, which is expanded and solidified to form a rigid polyurethane foam.

Among them, the o-toluenediamine polyether polyol used in Example 6 was obtained by using substantially the same procedure as in Example 5, and the preparation process was different only in that no water was added. The formulations of Examples 6-12 are shown in Table 1. The temperature of each component before mixing was controlled at 21 °C.

Table 1

The materials used in Examples 6-12 are described below:

The oleyl ether is: a fatty acid ester-containing polyol, and the NJ-4110D produced by Jurong Ningwu Co., Ltd. is specifically used in the examples.

The sucrose-initiated polyol is: sucrose and a small amount of water-initiated polyol, and the specific example used is NJ-8238 produced by Jurong Ningwu Company.

MDA-100 initiated polyol: made of 4'4-diaminodiphenylmethane as a starter by addition of propylene oxide, hydroxyl value, 360 mgKOH/g. The specific preparation process can be carried out by referring to the method for preparing the polyether polyol in Example 1, except that the o-phenylenediamine in Example 1 is replaced with 4'4-diaminodiphenylmethane.

Surfactant: L6863 silicone oil, produced by Momentive.

Mixed catalyst: a mixture of dibutyltin dilaurate, triethylenediamine, N,N-dimethylcyclohexylamine in a mass ratio of 1:1.2:1.2.

Polyisocyanate: PM-200, produced by Wanhua Chemical.

Foaming agent CP: cyclopentane, melon cyclopentane chemical production.

The foams prepared in Examples 6-12 were measured for cream time, gel time, free rise density, compressive strength, thermal conductivity, and demolding for 5 minutes. The test results are shown in Table 2.

Table 2

According to the test results, Examples 8, 9, and 10 had better compressive strength, demolding expansion, approximate thermal conductivity, and free rise density than those of Example 6 and Example 7. Example 11 had much worse compressive strength, thermal conductivity, and demolding expansion than Example 6. Example 12 has superior compressive strength and thermal conductivity than Example 6 and Examples 8, 9, and 10.

Those skilled in the art will appreciate that many modifications or adaptations of the present invention can be made in the teachings of the present disclosure. Such modifications or adaptations are also intended to be within the scope of the appended claims.

Claims

A method for preparing an amine-based polyether polyol, characterized in that an aqueous solution of an amine is subjected to an autocatalytic reaction with a part of an oxidized olefin, and then a catalyst is added, and the remaining oxidized olefin is added to an amine for epoxidation;

The amine contains 90% by mass or more of phenylenediamine.
The method for producing an amino polyether polyol according to claim 1, wherein the phenylenediamine is at least one of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
The method for producing an amino polyether polyol according to claim 1 or 2, wherein the amine contains 90% by mass or more of o-phenylenediamine and 10% by mass or less of other amines. A compound; preferably, the amine is o-phenylenediamine.
The method for producing an amino polyether polyol according to any one of claims 1 to 3, wherein the autocatalytic reaction is carried out at 130 ° C or lower, preferably at 105 ° C or lower, more preferably at 95 ° C or lower. get on;
The method for preparing an amino polyether polyol according to claim 4, wherein the autocatalytic reaction is carried out at a temperature lower than 100 ° C, after the autocatalytic reaction, and before the addition of the catalyst, the temperature is raised to The aging reaction is carried out at 100 ° C or higher, and preferably the temperature is raised to 100 to 115 ° C to carry out an aging reaction.
The method for producing an amino polyether polyol according to any one of claims 1 to 5, wherein the remaining olefin oxide and the amine are subjected to an epoxidation reaction at 100 ° C to 170 ° C, preferably at 110 The epoxidation reaction was carried out at -130 °C.
The method for producing an amino polyether polyol according to any one of claims 1 to 6, characterized in that the dehydration operation is carried out before the addition of the catalyst, or the dehydration operation is carried out before the addition of the alkylene oxide remaining after the addition of the catalyst .
The method for producing an amino polyether polyol according to any one of claims 1 to 7, wherein a molar ratio of a part of the alkylene oxide to the amine to be added is 1-4:1, preferably 3-3.8: 1.
The method for producing an amino polyether polyol according to any one of claims 1 to 8, wherein the amine polyether polyol has an equivalent weight per active hydrogen atom of 50 to 200, preferably 80-125.
The method for producing an amino polyether polyol according to any one of claims 1 to 9, wherein the oxidized olefin is one or a mixture of two of propylene oxide and ethylene oxide.
The method for preparing an amino polyether polyol according to any one of claims 1 to 10, wherein the catalyst is a strong base or an amine catalyst; preferably, the catalyst is used in a polyether polyol. 0.2-0.4% by weight of the product.
The method for preparing an amino polyether polyol according to any one of claims 1 to 11, characterized in that the adduct obtained by the preparation method has an average of 3.5-4 hydroxyl groups per molecule, 0- 0.5 secondary amino groups, 0-0.05 primary amino groups.
An amine-based polyether polyol obtained by the production method according to any one of claims 1 to 12.
A polyol composition for producing a polyurethane foam, characterized in that the polyol composition contains 10% by mass or more of the aminopolyether polyol according to claim 13.
The polyol composition for preparing a polyurethane foam according to claim 14, wherein the polyol composition further comprises one or more of a polyester polyol and another polyether polyol;

Preferably, the other polyether polyol is a mixture of one or more of oleyl ether, polyether polyol with sucrose as a starting agent, and polyether polyol with MDA-100 as a starting agent.
The polyol composition for producing a polyurethane foam according to claim 15, wherein the polyol composition comprises the following components by mass: the aminopolyether polyol of claim 13. 30-60%, 15-40% of polyether polyol with sucrose as initiator, 0-30% of polyether polyol with MDA-100 as initiator, and 5-40% of oleyl ether;

Preferably, the polyether polyol having MDA-100 as a starting agent accounts for 10-30% by mass in the polyol composition.
A method for preparing a polyurethane foam, comprising the steps of:

1) forming a mixture comprising: a polyol composition according to any one of claims 14-16, at least one blowing agent, at least one polyisocyanate, at least one catalyst, at least one surface active Agent

2) placing the mixture to expand and solidify the mixture to form a rigid polyurethane foam Under conditions.
The method for preparing a polyurethane foam according to claim 17, wherein the polyisocyanate is used in an amount of from 1.0 to 1.3 based on the equivalent of the polyol composition; based on 100 parts by weight of the polyol composition, a blowing agent, a catalyst, The amount of the surfactant used is 10-20 parts, 1-4 parts, and 0.01-6 parts, respectively.